Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
  • C08F291/02—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to elastomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
  • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols

Definitions

• the present invention relates to novel aromatic polyvinyl compounds and a method for the preparation thereof.
• an aromatic polyvinyl compound having two or more vinyl groups such as divinyl benzene, trivinyl benzene and the like are well known.
• the commonly known compounds having two or more vinyl groups include polyene-hydrocarbons, unsaturated esters of acrylic acid (e.g. allyl acrylate, crotyl acrylate) and acrylic esters of polyols.
• This kind of compounds has been used as a peroxide coagent in crosslinking of rubber and as a crosslinking agent in molding of unsaturated polyesters. Further, these compounds have been used as a crosslinking agent for crosslinked polymers such as crosslinked polystyrene beads and applied to ion-exchange resins, macro porous polymeric adsorbents and the like.
• these well-known compounds are not always satisfactory in terms of handling or the physical properties of articles prepared therefrom.
• most of the well-known compounds are liquid at room temperature and easily evaporate with a characteristic odor. Therefore, when they are used as a crosslinking agent for unsaturated polyesters or elastomers, their vapors are ready to leak and give an offensive odor in use.
• ester compounds resulting from hydroxystyrene compounds and polycarboxylic acids have an excellent property as a crosslinking agent for elastomers, resins for molding or paints, and are suitable for the preparation of crosslinking polymers having different degrees of flexibility. Further it was found that, when they are used as a plasticizer in a rubber processing, they exhibit an excellent plasticizing effect and moreover effectively serve as the so-called crosslinking plasticizer which improves the physical properties of vulcanized rubber by the reaction between the plasticizer and the rubber in the course of vulcanization.
• the ester compounds can be used not only for crosslinking but also for many other applications. The most remarkable characteristics of the ester compounds consist in an extremely low degree of volatility and freedom from an offensive odor in handling.
• the present invention provides a novel aromatic polyvinyl compound of the formula (1), ##STR4## wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are individually a hydrogen atom or a C 1 -C 20 alkyl group, A is a hydrocarbon residue, and n is an integer of 2 or 3, provided that when R 1 is a methyl group and each of R 2 , R 3 , R 4 , R 5 , R 6 and R 7 is a hydrogen atom, the isopropenyl group ##STR5## is located at o- or m-position to the oxycarbonyl group ##STR6## and a method for producing said novel aromatic polyvinyl compound of the formula (1), which comprises reacting a phenol compound of the formula (2), ##STR7## wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined above and M is a hydrogen atom or an alkali metal belonging to Group
• a and n are as defined above and Y is a hydroxyl group, a C 1 -C 20 alkoxy group or a halogen atom, in the presence or absence of a suitable catalyst.
• the present invention also provides a rubber composition
• a rubber composition comprising at least one of ester compounds of the formula (I), ##STR8## wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are individually a hydrogen atom or a C 1 -C 20 alkyl group, A is a hydrocarbon residue and n is a integer of 2 or 3.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 is as follows: R 1 , R 2 and R 3 are each a hydrogen atom, a methyl, ethyl, n-propyl or isopropyl group and R 4 , R 5 , R 6 and R 7 are each a hydrogen atom or a methyl group.
• the most preferred combination is as follows: R 1 , R 2 and R 3 are each a hydrogen atom or a methyl group and R 4 , R 5 , R 6 and R 7 are each a hydrogen atom.
• the hydrocarbon residue represented by A may be any, and is preferably an aliphatic residue having 1 to 20 carbon atoms or a residue containing at least one benzene nucleus, and more preferably an aliphatic residue having 1 to 10 carbon atoms or a C 1 -C 20 hydrocarbon residue containing at least one benzene nucleus.
• a tetramethylene, trimethylene, phenylene, biphenylene group and the like there are exemplified.
• the n is, in general, 2.
• the vinyl group represented by ##STR9## is preferably located at the meta position to the oxycarbonyl group, ##STR10##
• o-Vinylphenol m-vinylphenol, p-vinylphenol, o-isopropenylphenol, m-isopropenylphenol, vinylcresols, isopropenylcresols, isopropenyl-vinyl phenols, isopropenyl-isopropyl-phenols, tert-butyl-vinyl-phenols, isopropenyl-nonyl-phenols, ethyl-vinyl-phenols, ethyl-isopropenyl-phenols, dimethyl-vinyl-phenols, ethyl-methyl-vinyl-phenols, dimethyl-isopropenyl-phenols, ethyl-isopropenyl-methyl-phenols and alkali metal salts thereof.
• polycarboxylic acids and the reactive derivatives thereof represented by the formula (3)
• the compound of the formula (1) can be prepared by mixing the phenol compound of the formula (2) and the polycarboxylic acid or reactive derivative thereof of the formula (3) in an organic solvent or in water and heating the resulting mixture in the presence or absence of a suitable catalyst.
• polycarboxylic acid halides [corresponding to the formula (3) wherein Y is a halogen atom] and phenols [corresponding to the formula (2) wherein M is a hydrogen atom].
• the compounds of the formula (1) can easily be obtained by mixing phenols of the formula (2) and polycarboxylic acid halides of the formula (3) in an organic solvent capable of dissolving the two components, with no heating.
• bases such as N,N-dimethylaniline, triethylamine and the like.
• this reaction can easily be carried out by dissolving the sodium, potassium or lithium salt of phenol compounds represented by the formula (2) in water and the halide of polycarboxylic acids represented by the formula (3) in an organic solvent which is immiscible with water, and contacting the both solutions at the interface thereof.
• the organic solvents immiscible with water can properly be selected from hydrocarbons, halogenated hydrocarbons, ketones, ethers and the like.
• Heating is not particularly required for the reaction and good results are obtained at a temperature of less than 50° C, but it is sometimes necessary to heat the reaction solution to some degree in the vicinity of the end point of the reaction, depending upon the kind of compounds of the formula (2).
• a trace amount of stabilizers such as sodium hydrosulfite or cuprous chloride.
• the reaction comes to an end in 3 to 4 hours in general.
• the objective product can be isolated by removing the aqueous layer from the reaction mixture and evaporating the solvent from the organic solvent layer. Prior to evaporating the organic solvent, it is preferred to wash the organic layer with an alkali and water in order to remove the unreacted materials.
• the product thus obtained is almost pure so that further purification such as recrystallization is not necessary. However, when pure products are required, it can be achieved by recrystallization from a suitable solvent such as alcohol or ketone.
• the aromatic polyvinyl compounds synthesized by the method of the present invention are solid in general and are very widely used as an aromatic polyvinyl monomer.
• the novel aromatic polyvinyl compounds obtained from m-vinylphenols having the vinyl group ##STR11## at m-position to the oxycarbonyl group ##STR12## e.g. m-vinylphenol, m-isopropenylphenol and the like
• salts thereof as the phenols represented by the formula (2) have favorable physical properties suitable for a wide range of application as compared with the corresponding o- or p-isomers.
• the compounds resulting from the m-vinylphenols generally have a melting point lower than that of the corresponding p-isomers, and therefore a larger number of compounds which melt at required temperatures with a suitable flowability can be produced than in the case of the p-isomers.
• o- and p-vinylphenols are extremely unstable as compared with m-vinylphenols and easily polymerize into tar. It is apparent therefore that preparation of the compounds from m-vinylphenols is much easier than that of the o- and p-isomers.
• the vinyl group of the o- and p-isomers is unstable as compared with that of the m-isomers so that o- or p-isomers easily polymerize during storage or operations such as processing and kneading, thus changing in properties, while the m-isomers give a desirable crosslinkability only at a designed temperature.
• the compounds of the present invention can be used as a crosslinking agent for resins in reinforcement of paints and molded products, and also they are used as a crosslinking agent for elastomers. Further, in a polymer synthesis, good crosslinked polymers can be obtained by copolymerizing a compound of the formula (1). Particularly, the ester compounds of the formula (I) exhibit an excellent plasticizing effect in a rubber processing and moreover they serve effectively as the so-called crosslinking plasticizer which improves the physical properties of vulcanized rubber by the reaction of the plasticizer and the rubber in the course of vulcanization.
• the rubber used in the present invention may be any of natural rubbers and synthetic rubbers, for example, isoprene rubbers such as NR and IR, butadiene rubbers such as BR, SBR and NBR, olefin rubbers such as IIR, EPR and EPDM and elastic elastomers such as EVA.
• isoprene rubbers such as NR and IR
• butadiene rubbers such as BR, SBR and NBR
• olefin rubbers such as IIR, EPR and EPDM
• elastic elastomers such as EVA.
• an amount of the ester compound of the formula (I) to be added to the rubber depends upon the kinds of the rubber and the crosslinking plasticizer, and the use of the vulcanized rubber products.
• the amount is generally 1 to 30 parts by weight, preferably 2 to 20 parts by weight, based on 100 parts by weight of the rubber, in terms of the plasticizing effect and the physical properties of the vulcanized products.
• the ester compound of the formula (I) may be applied for a simple sulfur vulcanization of rubber, but it is more desirable to be applied for a peroxide vulcanization of the rubber, because polymerization of the plasticizer itself and crosslinking of the rubber by the plasticizer are effectively carried out using a free radical catalyst particularly an organic peroxide. Further, other compounding ingredients, for example other crosslinking agents, fillers, reinforcing agents, antioxidants and the like may be added.
• the vulcanization conditions of the compounded rubber depend upon the compounding and vulcanization system and are generally carried out at a temperature of 100° to 200° C for about 5 to 60 minutes. When the vulcanization is carried out by injection molding, a period of 2 to 3 minutes is sufficient.
• the most remarkable characteristic of the present invention consists in blending the rubber with the ester compound of the formula (I) as a crosslinking plasticizer.
• the rubber compositions thus obtained are superior to those containing no plasticizer and the compositions containing a common plasticizer such as a process oil. That is, they show extremely large tensile strength and tensile stress after vulcanization as well as very low extraction into solvents such as benzene, and exhibit little or no migration of oils to the surface of vulcanized products nor blooming.
• ester compounds of the formula (I) used in the present invention are solid at room temperature and have at least two rigid aromatic nuclei. Therefore they are very easy to handle in processing as compared with the well-known acryl or methacryl ester type crosslinking plasticizers, and give extremely improved heat resistance and stress at high temperatures to the vulcanized rubber.
• Example 2 To the same apparatus as in Example 1 were added 240 ml of water, 2.4g (0.06 mole) of sodium hydroxide, 0.02g of sodium hydrosulfite, 0.05g of trimethylbenzylammonium chloride and 6.71g (0.05 mole) of m-isopropenylphenol. The mixture was made a complete solution. Thereafter, 120 ml of a solution of 4.58g (0.025mole) of adipic acid chloride in methylene chloride was added dropwise from the dropping funnel at room temperature over 10 to 15 minutes during which the solution in the flask was violently stirred. After completion of the addition, the reaction solution was stirred at room temperature for about 2 hours and then at 40° C for 1 hour while refluxing the methylene chloride.
• Example 2 To the same apparatus as in Example 1 were added 240g of water, 2.4g (0.06 mole) of sodium hydroxide, 0.02g of sodium hydrosulfite, 0.05g of trimethylbenzylammonium chloride and 6.71g (0.05 mole) of m-isopropenylphenol. The mixture was made a complete solution. Thereafter, 120 ml of a solution of 5.99g (0.025 mole) of sebacic acid chloride in methylene chloride was added dropwise from the dropping funnel at room temperature over 10 to 15 minutes during which the solution in the flask was violently stirred. After completion of the addition, the reaction solution was stirred at room temperature for 2.5 hours and then at 40° C for 2 hours while refluxing the methylene chloride.
• the methylene chloride layer was separated and washed with two 200 ml portions of 5% aqueous sodium hydroxide solution and three 200 ml portions of water, and then dried over anhydrous calcium chloride. On evaporating the methylene chloride, bis-(3-isopropehylphenyl)sebacate was obtained as a pale yellow solid.
• reaction solution was washed with three 200 ml portions of 5% aqueous sodium hydroxide solution and two 200 ml portions of water, and then dried over anhydrous calcium chloride. On evaporating the xylene and recrystallizing from ethanol, bis-(3-isopropenylphenyl)terephthalate was obtained.
• test samples (A), (B) and (C), respectively] and the commercially available plasticizer as a reference were blended with the following rubber compound. Each blend was kneaded on a roller and vulcanized at 150° C for 20 minutes. The blank test was also carried out without the compounds or the plasticizer described above.
• the Mooney viscosity of the rubber compounds and the physical properties of the vulcanized products were measured according to JIS K 6300 and JIS K 6301, respectively. The results are shown in Table 1.
• the vulcanized products were extracted with benzene for 8 hours by means of a Soxhlet extractor. The results are shown in Table 1. The extraction ratio was calculated on the basis of the rubber compound for the blank test.
• the rubber compounds before vulcanization obtained in Example 1 were each mixed with carbon black and molded on an injection molding machine with an injection pressure of 1300 kg/cm 2 , an injection time of 1 minute, a vulcanization temperature of 170° C and a vulcanization time of 3 minutes.
• the molded product containing the process oil showed a bleeding phenomenon immediately after it was taken out of the mold and a tackiness on the surface thereof, while the molded products containing the present compounds did not show these phenomena.
• test sample (A) as the present compound and the common plasticizer and well-known ester compound as references were blended with the following rubber compound. Each blend was kneaded on a roller and vulcanized at 150° C for 4 minutes. The blank test was also carried out without the compounds described above.
• the rheometer test of the rubber compounds and the tension test and heat aging test of the vulcanized products were carried out according to JIS K 6301. The results are shown in Table 2.
• the maximum torque, T max obtained by the rheometer test is used as a measure of the stress at high temperatures and the retention obtained by the heat ageing test as a measure of the heat resistance.

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• Chemical & Material Sciences (AREA)
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• Chemical Kinetics & Catalysis (AREA)
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• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1976
  • 1976-06-03 CA CA254,038A patent/CA1083173A/en not_active Expired
  • 1976-06-03 FR FR7616758A patent/FR2313343A1/fr active Granted
  • 1976-06-04 DE DE2625332A patent/DE2625332C2/de not_active Expired
  • 1976-06-04 IT IT49815/76A patent/IT1066087B/it active
  • 1976-06-07 GB GB23455/76A patent/GB1498597A/en not_active Expired
  • 1976-06-07 US US05/693,695 patent/US4035559A/en not_active Expired - Lifetime

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